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Behavior of autoclaved magnesium oxysulfate cement pastes

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Adla Kellen Dionisio1,2 , Carlos Marmorato Gomes1
Pau dos Ferros Multidisciplinary Center, Rural Federal University of Semi-Árido, Brazil
Rural Federal University of Semi-Áridoa,1
a
BR 226, KM 405, São Geraldo – Pau dos Ferros – Rio Grande do Norte State, Brazil

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Abstract

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This study investigates the influence of autoclave curing on MOS cement
compared to acid addition effects, especially on microstructure and mechan-

er
ical properties. For this, compressive and flexural strength, water resistance
and volume stability were analysed. In addition, X-ray diffraction (XRD)
and Scanning Electron Microscopy (SEM) were applied to verify the phase
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composition and microstructure of these matrices. Results indicate that the
autoclave process affects the mechanical properties. The increase in the
molar ratio reduces flexural strength and slightly increases the compressive
strength. The autoclave also reduces water resistance, especially with in-
creasing curing time. Longer autoclaving time (4 hours) increases expansion
in the pastes, which stabilise in around 30 days. In the microstructure, au-
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toclaving reduces or inhibits the formation of the 517 phase and provides
the formation of the Mg(OH)2 and 512 or 513 phase. Therefore, despite the
autoclave process improvement properties on Portland cement, this process
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does not improve the properties of MOS cement without addition. Also, the
increase in autoclave time provides the formation of 512 or 513 phases.
Keywords: Magnesium Oxysulfate Cement, Mechanical properties, XRD,
SEM.
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Email address: adla.sousa@ufersa.edu.br (Rural Federal University of

Semi-Árido)
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URL: www.ufersa.edu.br (Rural Federal University of Semi-Árido)

1
Department of Architecture and Construction, Unicamp, Brazil
2
Department of Engineering and Technology, Rural Federal University of Semi-Árido,
Brazil
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Preprint submitted to Construction and Building Materials July 5, 2022

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1 1. Introduction

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2 Environmental concerns have increased the development of alternative
3 cements, such as magnesium oxide-based (MgO) composites. MgO-based
4 cement causes a lower environmental impact on ecosystems and resources
5 than Portland cement [1]. Thus, depending on MgO used, MgO-based cement
6 may be a sustainable product [2].
Magnesium oxysulfate cement (MOS cement) - one of the types of MgO-

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7

8 based cement - may be used to produce both refractory and non-refractory

9 materials. The production of light boards, used in dry construction, is its
10 main application [3, 4] due to the advantages of low density, good fire resis-
tance [5–7] and low thermal conductivity [6, 8]. In addition, MOS cement

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11

12 has high mechanical strength and elasticity [9] and, also may be used with
13 other materials such as fibre, pigments or admixtures that may change colour
14

15

16
and/or provide different characteristics.
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In MOS cement, the main factor that acts on the mechanical properties
is the formation of 5-phase, which influences volume stability. This phase
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17 also provides better water resistance. The lower water resistance is the main
18 disadvantage of this material, due to the dissolution or expansion of the
19 phases in the microstructure. In this way, the curing condition can affect the
20 microstructure and properties of MOS cement, which can influence water
21 resistance and volume stability.
In Portland cement, curing condition influences the properties. In this
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22

23 regard, studies [10–12] show that compressive strength increases in cementi-

24 tious systems based on Portland cement subjected to autoclave curing. The
25 autoclave curing process is a type of steam curing under high temperature
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26 and pressure, normally carried out in the temperature range between 160-
27 200◦ [13]. Thus, autoclave curing may accelerate the production of light
28 boards of MOS cement.
29 In this study, MOS cement pastes with different MgO/MgSO4 molar ra-
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30 tios were analysed regarding the influence of the molar ratio on autoclaved
31 MOS cement, aiming at better mechanical properties and microstructure.

32 2. Materials and methods

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33 2.1. Raw Materials

34 This study used the following raw materials: magnesium oxide (MgO),
35 magnesium sulfate heptahydrate (Epsom salt – MgSO4 ·7H2 O) and water.
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Table 1
Chemical composition of MgO.

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Mass fraction (%)
Sample
MgO SiO2 Al2 O3 Fe2 O3 CaO MnO
MgO 91.74 3.99 0.21 2.14 1.75 0.17

36 MgO used was calcined under ≈1.200◦ C, from IBAR Nordeste Ltda, with

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37 reaction time of 180s with acetic acid. The chemical composition of MgO
38 is shown in Table 1, whose main constituent is MgO and in lower amount
39 silicious dioxide, aluminium oxide and other compounds. Particle size distri-
40 bution and X-Ray diffraction pattern (XRD) of MgO is shown in Fig.1. The

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41 average diameter of particle size distribution was D(10) = 4.85 µm; D(50) =
42 23.5 µm; and, D(90) = 62.5 µm. The specific surface was determined by the
43

44

45
BET method, which resulted in 7.25 m2 /g.
A commercial magnesium sulfate heptahydrate (Epsom salt – MgSO4 ·7H2 O)
salt with purity of ≈ 97%, were purchased.
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1 0 0 10000 MgO
C u m u la tiv e p e r c e n ta g e ( % )

8 0 8000
Intensity (Counts)

6 0 6000
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4 0 4000

2 0 2000
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0 0
0 .1 1 1 0 1 0 0 1 0 0 0
10 20 30 40 50 60 70 80
D i a m e t e r ( µm ) 2-Theta (°)

(a) (b)

Fig. 1. Characterization of MgO: (a) Particle size distribution and (b) X-Ray diffraction
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pattern.

46 2.2. Preparation of MOS cement

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47 Table 2 shows MOS cement compositions. The samples were produced

48 with molar ratio MgO/MgSO4 (M) at 12, 13 and 14. The percentage of
49 MgSO4 in the solution was set at 25% based on other studies [14, 15] and
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Table 2
Compositions of MOS cement

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MgO/MgSO4 MgSO4 H2 O/MgSO4
Cure
molar ratio in solution (%) molar ratio (%)
air
12 25 20
autoclave
air
13 25 20

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autoclave
air
14 25 20
autoclave

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50 because percentages below 25% provide only 3-phase formation. The molar
51 ratio H2 O/MgSO4 was defined as 20% based on the literature [15, 16].
52

53

54
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MOS cement was produced considering the procedure as follow: (1) dilu-
tion of Epsom salt into the water to form a solution at 25% of MgSO4 using
a magnetic stirrer with a speed rating of 5 and a heating rate of 70%; (2)
Blend of MgSO4 solution and the MgO powder in a mixer; (3) casting of the
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55

56 pastes in prismatic moulds. Three prismatic specimens of each composition

57 with dimensions of 40×40×160 mm and samples of M equal to 12 and 14
58 with dimensions of 5×25×285 mm were cast.
59 After demoulding, samples were subjected to cure. Three different curing
60 regimes (Fig. 2) were adopted in this study, as follows:
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61 (a) Curing regime A (Fig. 2(a)): curing in air at ambient temperature

62 22±5◦ C and relative humidity of about 50% until tests at 28 days;
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63 (b) Curing regime B (Fig. 2(b)): air curing by 24 hours (demoulding time),
64 followed by autoclave curing by 2 hours at 1 atm pressure and tempera-
65 ture of 120±5◦ C, and
66 (c) Curing regime C (Fig. 2(c)): air curing by 24 hours (demoulding time)
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67 + autoclave curing by 4 hours at 1 atm pressure and temperature of

68 120±5◦ C.

69 2.3. Testing procedure

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70 The flexural and compressive strengths of samples were tested according

71 to ASTM C348 [17] and ASTM C349 [18] on a hydraulic machine, using
72 a maximum force of 100 kN. The compressive strength was obtained using
73 portions of prisms broken in flexure. Three specimens were analysed at
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Temperature (°C)
22 ± 5

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0 Test age
Time(h)

(a) Curing regime A

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120 ± 5
2h

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4h
Temperature (°C)

Temperature (°C)
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24h 24h
22 ± 5 22 ± 5

0 Time to reach Cooling time and Test age 0 Time to reach Cooling time and Test age
1 atm pressure pressure drop 1 atm pressure pressure drop
Time(h) Time(h)
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(b) Curing regime B (c) Curing regime C

Fig. 2. Representation of curing regimes.

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74 ambient curing (curing regime A) and another three samples at autoclave

75 curing (curing regime B or C).

76 2.4. Microstructure analysis

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77 X-ray diffraction (XRD) and Scanning electron microscopy (SEM) were

78 used to study the microstructure at 28 days. XRD was used to analyse the
79 mineralogical composition of pastes and was carried out using a Rigaku Mini-
80 Flex II X-ray diffractometer with Cu-K radiation source, operated at 30 kV,
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81 15 mA, scanning rate of 4◦ /min and 2θ range from 7◦ to 80◦ . Electronic mi-
82 croscopy was performed using fractured samples. This analysis was perform
83 in samples with molar ratio equal to 12 in a LEO 430i microscope, coupled
84 to an Oxford Instruments Energy Dispersive X-ray Spectrometer (EDS). In
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85 the MOS cement with molar ratio equal to 13 and 14 was performed in a

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86 LEO 440i microscope, with an Energy Dispersive X-ray Spectrometer (EDS),
87 model 6070 of the LEO Electron Microscopy/Oxford (Cambridge, England).

88 3. Results and discussions

89 3.1. Effect of autoclave curing on mechanical properties

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90 Autoclave curing affects the flexural and compressive strength of MOS
91 cement. There is a tendency to improve compressive strength with an in-
92 creasing molar ratio (Fig. 3).

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1 0
0 h 3 5 0 h
2 h 2 h
4 h 4 h
8

er C o m p r e s s iv e s tr e n g th ( M P a )
3 0
F le x u r a l s tr e n g th ( M P a )

2 5
6
2 0
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4 1 5

1 0
2
5

0 0
1 2 1 3 1 4 1 2 1 3 1 4
M g O /M g S O m o la r r a tio M g O /M g S O m o la r r a tio
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4 4

(a) Flexural strength (b) Compressive strength

Fig. 3. Effect of autoclave curing on flexural and compressive strength.

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93 The flexural strength of MOS cement increases with increasing autoclave

94 time and molar ratio MgO/MgSO4 (Fig. 3(a)). In the cement submitted to
95 ambient curing, the flexural strength in the samples with a molar ratio equal
96 to 12, 13 and 14 were 2.28, 4.14 and 2.52 MPa, respectively.
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97 After the curing in the autoclave, there is a tendency for values to in-
98 crease in the samples. In pastes with a MgO/MgSO4 ratio of 12, the flexural
99 strength of MOS cement subjected to 2 hours and 4 hours in the autoclave
100 was 7.70 and 6.88 MPa, respectively, an increase of about 5.42 and 4.6 MPa.
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101 The highest result was for the MgO/MgSO4 ratio equal 13 autoclaved for 4h.
102 Increasing the molar ratio decreased flexural strength. However, the flexural
103 strength values submitted to autoclave were higher than those submitted to
104 ambient cure.
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105 Regarding compressive strength (Fig. 3(b)), in the control samples, sub-

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106 mitted to ambient cure, the results for molar ratio equal to 12, 13 and 14
107 were 17.92, 25.39 and 25.78 MPa, respectively. In MOS cement M12, au-
108 toclaved for 2 and 4 hours, the compressive strength results were 22.02 and
109 26.88 MPa. For example, comparing these values with samples submitted
110 to ambient curing, there was an increase of about 22.88% and 50%, respec-
111 tively. In general, the compressive strength of the mixtures increased with

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112 the increase of the molar ratio and samples submitted to autoclave curing
113 showed better results.
114 In Portland-based cement materials, the vantage of autoclave using is
115 obtaining after 24 hours a compressive strength similar to reach to 28 days for

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116 samples subject to ambient curing, reduction of shrinkage and efflorescence
117 elimination [19–21].In MOS cement, in general, the results of mechanical
properties were higher in samples submitted to autoclave curing. This show
118

119

120

121
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that the autoclaving process provides an increase in mechanical properties.
The mechanical properties in MOS cement are related to phase formation,
mainly the 5-phase. [2, 15, 22]. The autoclaving process may have provided
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122 a denser microstructure, with less Mg(OH)2 formation and the development
123 of the 5-phase. The formation of Mg(OH) 2 occurs when MgO reacts with
124 water, causing an expansive hydration reaction due to the density difference
125 between MgO (3.5 g/cm3 ) and Mg(OH)2 (2.4 g/cm3 ) [23]. Thus, the higher
126 values of mechanical properties are due to the presence of 5-phase and low
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127 formation of Mg(OH)2 .

128 In MOS cement, studies [2, 24] have shown that the use of acid improves
129 the mechanical properties, with results of compressive strength above 100
MPa. The acid could inhibit the hydration of MgO - to form Mg(OH)2 [22]
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130

131 and provide more phase formation, mainly 5-phase. Furthermore, the use
132 of siliceous materials such as mineral admixtures could improve mechanical
133 properties.
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134 3.2. Effect of autoclave curing on water resistance

135 Immersion of samples in water affects the reduction of compressive strength
136 in MOS cement (Fig. 4). The best performance after exposure to water was
137 in the samples submitted to 2h of autoclaving to M equal 12 and 14.
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138 In sample M equal to 12, the compressive strength without and after im-
139 mersion was 17.92 and 15.08 MPa, respectively, a reduction of 15.85%. MOS
140 cement with M equal 14 compressive strength was 26.88 and 23.91 without
141 and after immersion, respectively, a reduction of 11,05%. These reductions
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1 .0
3 5 W ith o u t im m e r s io n
A fte r im m e r s io n

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W a te r r e s is ta n c e c o e ffic ie n t
3 0 0 .9

C o m p r e s s iv e s tr e n g th ( M P a )

W a te r r e s is ta n c e c o e ffic ie n t
2 5
0 .8
2 0

1 5 0 .7

1 0
0 .6

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5

0 0 .5
0 h 2 h 4 h 0 h 2 h 4 h 0 h 2 h 4 h
1 2 1 3 1 4
M g O /M g S O 4 m o la r r a tio

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Fig. 4. Compressive strength and water resistance coefficient of MOS cement with 28 days
and after water immersion.

142

143
may indicate the presence of unreacted MgO, which after immersion may
have reacted with water to form Mg(OH)2 . Thus, immersion in water affects
the strength and contributes to decrease water resistance. Wang et al. [24]
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144

145 relate that the formation of Mg(OH)2 in addition to the existing contributes
146 to the reduction of water resistance.
147 There is a tendency to water resistance increase in samples submitted to
148 autoclave curing. In MOS cement MgO/MgSO4 equal 12 subjected to 2 hours
149 of autoclave curing, the water resistance was higher than in sample submitted
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150 to ambient curing. In this sample, the compressive strength without and after
151 immersion was 25.39 and 24.02 MPa, respectively, a decrease of 5,40%, lower
152 than the sample subjected to ambient curing. In the MOS cement submitted
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153 to autoclave cure for 4 h the decrease in compressive strength was higher.
154 The same behaviour occurs in M equal to 13 and 14.
155 Regarding water resistance coefficient, was higher for M equal to 12 auto-
156 claved for 2 hours, whose reduction in compressive strength was lower after
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157 water immersion. The higher value is due to the immersion time in water, of
158 24 hours. The increase in immersion time may reduce the water resistance
159 coefficient and cause disintegration of MOS cement [8]. In general, the bet-
160 ter result of αr was to MOS cement submitted to 2 hours of autoclaving and
molar ratio of 12.
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161

162 The decrease in water resistance may be due to the dissolution of phase-5
163 [22]. The main phase which improves mechanical properties and water resis-
164 tance is phase-5 [25]. Thus, besides the formation of Mg(OH)2 , due to late
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165 MgO reaction, there may have occurred dissolution of phase-5 in MOS ce-

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166 ment. The unreacted MgO, when hydrated - due to stress of crystallisation
167 - may cause expansion and instability of the microstructure [26]. Delayed
168 hydration of MgO may cause an expansion in the MOS cement, which can
169 cause damage such as cracks or fractures. Furthermore, in water immersion,
170 the phases can decompose into molecules of Mg(OH)2 , H2 O and soluble ions,
171 which may be carried towards the surface of the hardened paste [27]. An-

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172 other ion that can be released is the sulfate ion (SO2−
4 ), which can damage
173 the structure of the MOS cement. This instability in the microstructure
174 influences the water resistance and, consequently, the water resistance coef-
175 ficient. Therefore, phase dissolution also causes damage to the MOS cement

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176 and affects its mechanical performance.
177 Despite the reduction in compressive strength after water immersion,
probably due to the delay in MgO formation and phase dissolution, the
178

179

180

181
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higher αr was to M equal 12 submitted to 2 hours of autoclaving, whose wa-
ter resistance was higher than other samples. Another way to improve water
resistance is by using acid. The acid provides growing [28] and improves the
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182 5-phase stability [29].

183 3.3. Volume stability

184 The autoclaving process causes an expansion in the MOS cement, which
185 decreases with an increasing molar ratio (Fig. 5).
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0 .6 1 2 - 0 h 1 4 - 0 h
1 2 - 2 h 1 4 - 2 h
1 2 - 4 h 1 4 - 4 h
0 .4
tn V o lu m e s ta b ility ( % )

0 .2

0 .0
0 1 0 2 0 3 0 4 0
T im e ( d a y s )
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-0 .2

-0 .4

Fig. 5. Volume stability of MOS cement.

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186 In MOS cement, submitted to air curing mainly shrinkage occurred. At

187 M equal to 12, shrinkage occurred in the first 24 hours. After 48 hours, there
188 was an increase in shrinkage, which tended to stabilise after 30 days. On
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189 the other hand, in M equal 14, there was expansion in the first 48 hours

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190 and after this shrinkage occurred. In these samples, the higher shrinkage
191 was in the 42 days to M equal 12 (0,38%) and lower shrinkage to M equal
192 14 (0,28%). Thus, the increase in the M provoke a reduction in shrinkage
193 and volume stability tend to stabilise first. Increased shrinkage with time in
194 MOS cement has also been observed by other researchers [15, 30].
195 Autoclave curing on pastes resulted in an expansion in all samples. In the

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196 first 24 hours, the expansion is small, which refers to the moment that the
197 pastes are in the process of hardening, still in the moulds of the specimen.
198 After autoclave curing, an increase in expansion occurred, for which the
199 higher value was for the first measurement after the autoclave process.

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200 The higher value of expansion was for the samples that remained 4 hours
201 in the autoclave, i. e., the increase in the duration of the autoclaving process
increased expansion of the MOS cement. Then, there was a reduction in
202

203

204

205
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expansion, which tended to stabilise after 30 days. The high temperature
and pressure accelerated the MOS cement hydration process and, conse-
quently, reduced the hydration time - which, when prolonged, contributes to
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206 improving its mechanical resistance. This reduction in hydration time can
207 contribute to the formation of more Mg(OH)2 , which leads to lower phase
208 formation and development, especially the 5-phase.
209 In MOS cement shrinkage is related to chemical and drying shrinkage [30].
210 Chemical shrinkage is associated with the degree of hydration of the MOS
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211 cement and the hydration products formed. Denser hydration products with
212 greater degree of hydration result in greater chemical shrinkage [30]. On the
213 other hand, drying shrinkage occur in the hardened material due to the loss
of free water on drying [31].
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214

215 Concerning expansion in the MOS cement, the drying shrinkage and
216 strain – due to expansion – influence in the volumetric stability of MOS
217 cement [32]. In Portland cement, the MgO expansion – due to the forma-
218 tion of Mg(OH)2 – is locally contained by the cement matrix surrounding
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219 the compounds, this induces the expansive stress and expansion of the ma-
220 trix. This may have occurred in autoclaved pastes, whose higher value of
221 expansion occurred in the early ages (before the 3rd day of moulding) and
222 according to He et al. [33] is due to the hydration of MgO to form Mg(OH)2 .
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223 In the microstructure of Portland cement, crystals of Mg(OH)2 con-

224 tributes to decelerate hydration, which avoids the increase in temperature
225 - which causes the acceleration of shrinkage [34]. Thus, in MOS cement crys-
226 tals of Mg(OH)2 there may be acts to decelerate hydration process and causes
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227 little retraction at early ages. Hence, the formation of Mg(OH)2 may have

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228 provided low values of volume stability at early ages. On the other hand,
229 the increase in time caused an increase in shrinkage, reaching a plateau at
230 approximately 30 days.
231 Autoclaving caused expansion in samples, which tended to decrease with
232 the increase of the material age. The decrease in expansion in autoclaved
233 MOS cement may be due to the densification of the microstructure provided

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234 by the autoclaving process. This expansion is due to the loss of free water on
235 drying during and after the autoclaving process. In MOS cement, the greater
236 the porosity and the lower the strength of the material matrix, the greater
237 the loss of free water [15]. This may result in cracking and strain before the

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238 material be submitted to loading, which may have influenced the mechanical
239 strength in the autoclaved samples.

240

241

242
3.4. Phase composition
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Diffractograms (Fig. 6) shows that MOS cement contains MgO and
Mg(OH)2 , compounds also observed in other studies [2, 14, 35, 36].
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243 The presence of MgO indicates that part of it did not participate in the
244 hydration process and remained after hardening. Unreacted MgO may act
245 as a microaggregate, which fills pores and reduces porosity. In addition, the
246 presence of MgO, according to Wu et al. [37], may damage the mechanical
247 properties of cement due to contact with water e post-hardening hydration.
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248 This late hydration may result in dimensional variation, which explains the
249 decrease in compressive strength and water resistance.
250 The samples submitted to air curing, in addition to MgO and Mg(OH)2 ,
contain Epsom salt and 512 or 513 phase and, may have 3-phase and 517
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251

252 phase. The increase in a molar ratio to 13 (Fig. 6(b)) and 14 (Fig. 6(c))
253 caused a decrease in MgO, Mg(OH)2 and Epsom salt peaks and, there was
254 no formation of 3-phase peaks. This decrease in MgO and Mg(OH)2 (at
255 2θ of 42,6◦ and 62,0◦ ) peaks indicates the formation of other compounds.
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256 Thus, 5-phase peaks appeared and/or increased, which explains the increase
257 in compressive strength in specimens. At M equal to 14, 512- or 513-phase
258 phase peaks (at 2θ of 17,6◦ and 28,9◦ ) were smaller and more peaks of the
259 517 phase appeared (at 2θ of 9,7◦ ; 11,8◦ ; 17,8◦ , and 28,9◦ ). 3-phase appeared
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260 in M equal 12 at 2θ of 17,2◦ and 27,2◦ , whereas in M equal 13 and 14, its
261 formation did not occur. The presence of Epsom salt is due to the unreacted
262 salt. Regarding Epsom salt peaks, the increase in molar ratio MgO/MgSO4
263 caused a decrease (at 2θ of 20,5◦ and 32,6◦ ) or no formation (at 2θ of 20,5◦ ;
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MgO MgSO4.7H2O MgO MgSO4.7H2O
Mg(OH)2 512 or 513 phase Mg(OH)2 512 or 513 phase

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318 phase 517 phase 318 phase 517 phase

4h
4h

2h

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2h

0h 0h

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80

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2-Theta (°) 2-Theta (°)

(a) MgO/MgSO4 = 12 (b) MgO/MgSO4 = 13

er MgO MgSO4.7H2O
Mg(OH)2 512 or 513 phase
318 phase 517 phase
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4h

2h
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0h

10 20 30 40 50 60 70 80
2-Theta (°)
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(c) MgO/MgSO4 = 14

Fig. 6. Diffractograms of MOS cement.

37,5◦ and 50,3◦ ), which indicates that it reacted more. The smaller amount
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264

265 of Epsom salt with the increase of M may have contributed to this.
266 In the MOS cement submitted to the autoclaving process, the formation
267 of the same compounds occurred as in the MOS cement submitted to air
268 curing. In M equal to 12 (Fig. 6(a)), autoclave curing provided reducing in
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269 MgO, Mg(OH)2 and 3-phase and Epsom salt peaks disappearing. In addition,
270 there was the appearance of other peaks in the 3-phase (at 2θ of 17,2◦ e 22,8◦ )
271 and 512 or 513 phase (at 2θ of 11,4◦ ; 17,2◦ e 22,8◦ ). Still about sample M
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272 equal to 12, the increase in autoclaving time from 2 to 4 hours provided an

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273 increase in Mg(OH)2 peak, improvement and appearance of other 3-phase
274 and 512 or 513 phase peaks; and the reappearance of Epsom salt.
275 The increase in molar ratio associated with the autoclave process in-
276 creased MgO peaks, which become more acute, i. e., more closed. Regarding
277 formation phases, in M equal to 13 increased 3-phase and 512 or 513 phase
278 peaks and, appeared 5-phase (517 phase) peaks (at 2θ of 9,7◦ ; 11,8◦ ). The

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279 sample with M equal to 14 and a cure time of 2 hours was not observed of
280 512 or 513 phase peaks. On the other hand, the increase in curing time to
281 4 hours favored the presence of 512 or 513 phase and increased the 5-phase
282 peak (at 2θ of about 9,7◦ ; 11,8◦ ). Furthermore, in some samples subject to

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283 the autoclave process, there was a formation at 2θ of about 40◦ , which refer
284 to 512 or 513 phase alone or a 3-phase and 512 or 513 phase together. The
associated increase in molar ratio and autoclaving cure time reduced this
285

286

287

288
peak.
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The phases were identified based in studies of Dinnebier et al. [38] (318,
512 or 513 phases) and Runčevski et al. [39] (517 phase). Dinnebier et
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289 al. [38] report that 512 and 513 phases have identical reference patterns.
290 The patterns used to identify these phases were PDF 086–1322 [40] for 512
291 phase, PDF 07–0415 [41], PDF 00-013-0340 [42] and PDF 08–0280 [43] for
292 513 phase. The reference patterns used to identify 3-phase was: PDF 13–0339
293 [42], 07–0418 [44], 08–0281 [43]. The 517 phase was identified based on the
ot

294 study by [39]. Demediuk and Cole [42] report that 3-phase forms at low
295 temperature and 5-phase may form at both low and high temperature. In
296 MOS cement studied, 3- and 5-phase were observed at low temperature (air
curing), as verified by Demediuk and Cole [42].
tn

297

298 Thus, the presence of 3-phase in autoclaved samples indicates the forma-
299 tion of 3-phase before autoclaving the specimens and shows that this phase
300 remained after submitting MOS cement to the autoclaving process. More-
301 over, the autoclaving process increased the amount and intensity of 517 and
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302 512 or 513 peaks. It was also observed that increasing the molar ratio to
303 13 and 14 caused the formation of 517 phase peaks. Therefore, there is a
304 tendency to formation 512 or 513 phase under high temperature and pressure
305 and in an accelerated hydration process. The higher temperature in the au-
ep

306 toclave process may have provided a loss of hydration water from the pastes,
307 which afforded fewer water molecules.
308 In this way, acceleration in the hydration process – provoked by autoclave
309 – tends to form 512 or 513 phase and an increase in molar ratio form also
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310 517 phase. The presence of this phase in the pastes indicates that this phase

iew
311 has not dissolved. The 517 phase insoluble in water [8], therefore, in contact
312 with water, tends to behave better than the three-phase and 513 [2] or 512
313 phase, preventing its solubilization during the autoclave process.

314 3.5. Microstructure

315 The microstructure of MOS cement is shown in (Fig. 7). All the samples

ev
316 are composed by MgO and Mg(OH)2 . The increase in the molar ratio caused
317 the presence of Mg(OH)2 in higher amounts and 5-phase in fewer amounts.
318 The appearance of 5-phase with an increase in the molar ratio may be due
319 to a reduction in the amount of Epsom salt and, consequently, a lower water

r
320 ratio. The needle-like crystals formed in the cement paste are the 5-phase
321 – 5Mg(OH)2 .MgSO4 .7H2 O (5-1-7) or 5Mg(OH)2 .MgSO4 .2 or 3H2 O (5-1-2 or
3).
322

323

324

325
er
In MOS cement, hydration occurs quickly at first due to the rapid hy-
dration of MgO, thus creating an environment of low supersaturation, i. e.,
rapid evaporation of the saturated solution occurs. Crystals that grow under
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326 these conditions tend to be plaque-shaped [45]. This format is the form of
327 phase 318, produced at low temperature [42], which is the main phase in the
328 liquid phase of MOS cement [46]. The MgO rapid reaction may cause a vol-
329 ume variation of material, which may have influenced the volume stability
330 of the pastes (Fig. 5). The porous material may be damaged during the
ot

331 crystallisation process if there is a high crystallisation pressure [47].

332 At 28 days, the microstructure of air cured samples (Fig. 7 (a), (d) and
333 (g)) is also composed of 5-phase (517 phase and/or 512 or 513 phase) as
shown in the XRD. In M equal to 12 (Fig. 7(a)), there is a greater presence
tn

334

335 of Mg(OH)2 and a low amount of 5-phase. Increasing the molar ratio to
336 13 and 14 reduced the presence of Mg(OH)2 and increased the 5-phase, as
337 shown in the XRD. The higher 5-phase formation improved the compressive
338 strength at 28 days. According to XRD results, the 5-phase present in the
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339 sample Fig. 7(a) (M equal to 12) is 512 or 513 phase, while in the pastes with
340 M equal to 13 (Fig. 7(d)) and 14 (Fig. 7(g)) 5-phase they refer to 512 or 513
341 phase and 517 phase. In specimen M equal to 12, the 5-phase appear isolated
342 as shown in (Fig. 8(a)), with higher presence of Mg(OH)2 . The spectrogram
ep

343 (Fig. 8(b)) of this image shows higher intensity of magnesium (Mg) and
344 oxygen (O) peaks. In M equal to 13, 5-phase, despite not having developed,
345 was formed with a thick shape, 0.6µm, and an average length of 9.44µm.
346 In the MOS cement equal to 14, 5-phase was formed more distributed and
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 ed
iew
Mg(OH)2 3-phase
Mg(OH)2
Mg(OH)2
3-phase
5-phase

ev
(a) M12 - 0h (b) M12 - 2h (c) M12 - 4h

Mg(OH)2

Mg(OH)2
5-phase
5-phase

r
5-phase

(d) M13 - 0h er
(e) M13 - 2h (f) M13 - 4h
pe
Mg(OH)2 Mg(OH)2

Mg(OH)2 5-phase

5-phase
Mg(OH)2
5-phase
ot

(g) M14 - 0h (h) M14 - 2h (i) M14 - 4h

Fig. 7. Scanning Electron Microscopy images of MOS cement.

tn

347 appear in more quantity (Fig. 8(c)). The aspect of phase-5 in this sample is
348 thinner and has an average length of 7.78µm. The spectrogram (Fig. 8(d))
349 of this phase shows higher intensity of magnesium, oxygen, and sulfur (S)
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350 peaks.
351 In autoclaved MOS cement (Fig. 7 (e), (f), (h) and (i)), the curing process
352 increased Mg(OH)2 formation, which indicates greater hydration of MgO. In
353 addition, unreacted MgO may have hydrated after curing, phenomena also
ep

354 observed by [15]. In MOS cement with M equal to 12 autoclaved for 2 and
355 4 hours (Fig. 7(b)), there is formation, in addition to Mg(OH)2 , of the 3-
356 phase. Although not observing the 5-phase (512 or 513 phase) in this image,
357 it is present because it appears in the XRD. Increasing the molar ratio to 13
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 ed
iew
ev
(a) M12 - 0h (b) Spectrogram in Mg(OH)2

r
Counts
15000
Mg

er 10000

5000
O

Au
S
pe
S
Au
Ca
Fe Si Fe Au Au
Au Ca Fe
Ca Au Au Au Au
0
0 5 10 15 20
Energy (keV)

(c) M14 - 0h (d) Spectrogram in 5-phase

Fig. 8. SEM (10.000x) and spectrogram of air cured MOS cement: (a) and (b) M equal
ot

to 12; (c) and (d) M equal to 14.

and 14 enhanced the formation of 5 phases, but the increase in time in the
tn

358

359 autoclave to 4 hours caused a reduction in it. In M equal to 13 submitted to

360 2 hours in the autoclave (Fig. 7(e)), the needle crystals are thinner, have a
361 width of 0.19 - 1.35µm and a structure similar to a 5-phase core is observed.
362 In paste with a molar ratio equal to 14 autoclaved by 2 hours, overlap of the
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363 needle is observed (Fig. 9(a)). An EDS in the 5-phase (Fig. 9(b)) of this
364 image shows magnesium, oxygen, and sulfur; these elements are present in
365 ratios of 44.38%, 42.86%, and 7.22%, respectively. In pastes with 4 hours
366 of autoclave curing, the 5-phase formation was also affected. Therefore, the
ep

367 autoclaving process affected the development of a 5-phase core as crystal

368 and, consequently, crystal formation.
369 The rapid reaction of MgO with water to form magnesium hydroxide
370 contributed to lower compressive strength in the pastes, mainly in the au-
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 ed
Counts

iew
15000

Mg
O

10000

S
5000 Au
S Fe
Fe Au

ev
Mn
Mn Si Ca Fe Au Au
Ca Au Ca Mn Au Au Au Au
0
0 5 10 15 20
Energy (keV)

(a) SEM (10.000x) (b) EDS

r
Fig. 9. (a) SEM (10.000x) of M equal to 14 autoclaved by 2 hours and (b) spectrogram.

371

372

373
MgO with the SO2−
The concentration of the SO2−
er
toclaved samples. The quick formation of Mg(OH)2 inhibits the reaction of
4 ion to form the phases. Two factors influence that: (a)
4 ion in the sulfate solution, which is ≈ 2.93
mol/L [15]; and (b) The radius of the SO2−
4 ion, which is ≈ 3.79Å [48]. Thus,
pe
374

375 considering these two factors, the probability of SO2−

4 ion going towards the
376 hydrated MgO and reacting with it is low. In consequence, this reduces
377 the possibility to form more 5-phase and obtain better results of mechanical
378 properties.
ot

379 4. Conclusions
380 In this study, MOS cement with different molar ratios submitted to auto-
tn

381 clave curing is analysed concerning the effect on properties and microstruc-
382 ture. Autoclave curing interferes with MOS cement matrices. In this sense,
383 based on the results obtained, the following conclusions are drawn:

(i) The two-hour (2h) autoclave curing for a MgO/MgSO4 molar ratio of 12
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384

385 increased the flexural strength and showed better results than the other
386 molar ratios. An increase in cure time increases compressive strength
387 with an increase in molar ratio.
388 (ii) Water resistance reduces after water immersion. An increase in molar
ep

389 ratio causes a decrease in the water resistance coefficient.

390 (iii) Autoclave curing provides, at first, the expansion of the MOS cement
391 and, after one day of autoclave curing, the shrinkage start.
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 ed
392 (iv) The autoclave process accelerates the hydration of MOS cement and

iew
393 provides the formation of Mg(OH)2 and, mainly, of 512 or 513 phase.
394 An increase in molar ratio allows the appearance, albeit small, of phase
395 517, which provides an increase in compressive strength.

396 Therefore, there is a tendency to form the 512 or 513 phase at low temper-
397 atures. In addition, autoclave curing by accelerating the hydration process
inhibits the formation and growth of phase 517, which is the main phase

ev
398

399 contributing to the mechanical properties. Thus, the effects of acid addition
400 on MOS cement properties tend to be better than cement autoclave curing.

r
401 Acknowledgments
402 The authors would like to express their gratitude for the support from
403

404 er
PIBIC Unicamp and the National Council for Scientific and Technological
Development (CNPq - process 308881/2017-6).
pe
405 References
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ot

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